CN112694253A - Starting glass, lithium silicate glass with core, preparation method and application thereof - Google Patents
Starting glass, lithium silicate glass with core, preparation method and application thereof Download PDFInfo
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- CN112694253A CN112694253A CN202011564799.9A CN202011564799A CN112694253A CN 112694253 A CN112694253 A CN 112694253A CN 202011564799 A CN202011564799 A CN 202011564799A CN 112694253 A CN112694253 A CN 112694253A
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- Prior art keywords
- glass
- lithium silicate
- fluorescent
- core
- melting
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- 239000011521 glass Substances 0.000 title claims abstract description 68
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052912 lithium silicate Inorganic materials 0.000 title claims abstract description 35
- 239000005368 silicate glass Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 69
- 230000008018 melting Effects 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000919 ceramic Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 230000000171 quenching effect Effects 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000006121 base glass Substances 0.000 claims description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910019142 PO4 Inorganic materials 0.000 claims description 14
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 14
- 235000021317 phosphate Nutrition 0.000 claims description 14
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 13
- 239000003086 colorant Substances 0.000 claims description 12
- 239000002667 nucleating agent Substances 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 239000001062 red colorant Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000001060 yellow colorant Substances 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- USEGQPUGEPSVQL-UHFFFAOYSA-N [Pr].[Zr] Chemical compound [Pr].[Zr] USEGQPUGEPSVQL-UHFFFAOYSA-N 0.000 claims description 2
- DIVGJYVPMOCBKD-UHFFFAOYSA-N [V].[Zr] Chemical compound [V].[Zr] DIVGJYVPMOCBKD-UHFFFAOYSA-N 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- KHJHBFLMOSTPIC-UHFFFAOYSA-N prop-2-enylidenechromium Chemical compound C(=C)C=[Cr] KHJHBFLMOSTPIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000001054 red pigment Substances 0.000 claims description 2
- 239000006017 silicate glass-ceramic Substances 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000002994 raw material Substances 0.000 abstract description 50
- 230000000694 effects Effects 0.000 abstract description 38
- 229910052573 porcelain Inorganic materials 0.000 abstract description 14
- 239000000843 powder Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000010309 melting process Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 48
- 229910052697 platinum Inorganic materials 0.000 description 24
- 239000006060 molten glass Substances 0.000 description 22
- 238000005266 casting Methods 0.000 description 19
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003103 lithium disilicate glass Substances 0.000 description 14
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 11
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 5
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007499 fusion processing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910004116 SrO 2 Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005375 photometry Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/836—Glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0018—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents
- C03C10/0027—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
- C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Ceramic Engineering (AREA)
- Public Health (AREA)
- Crystallography & Structural Chemistry (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides starting glass, lithium silicate glass with a core, and a preparation method and application thereof, and belongs to the technical field of fluorescent materials. The lithium silicate glass with the core is prepared by uniformly mixing a basic glass component and a fluorescent component, melting and water quenching the mixture, and melting the water-quenched glass frit in an air atmosphere but no reducing atmosphere to obtain glass liquid; and pouring the obtained glass liquid into a specific mould for forming, cooling the formed porcelain block, and performing heat treatment to obtain the ceramic block. According to the preparation method provided by the invention, the compound of the fluorescent element is introduced into the raw material, no additional fluorescent powder is needed, the required fluorescent effect can be achieved without reducing atmosphere in the melting process, the process is simple, and the fluorescent color is easy to control. The obtained lithium silicate glass with the core can be effectively used for preparing dental prosthetic materials, and can simulate the effect of gradually changing the color of natural teeth from neck to cut off, thereby achieving the fluorescent effect similar to that of the natural teeth and effectively improving the aesthetic effect.
Description
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to starting glass, lithium silicate glass with a core, and a preparation method and application thereof.
Background
Lithium disilicate (Li)2Si2O5) The glass ceramic is widely applied in the field of dental restoration, has the transparency of glass and the strength of ceramic, has unique advantages in the aspect of aesthetic restoration, particularly has the advantages of minimally invasive restoration or ultrathin veneering, and has more obvious advantages compared with the traditional zirconia material due to the texture and opalescence of the lithium disilicate glass ceramic material.
Dental restorative materials often mimic natural teeth in all aspects, thereby achieving a simulated effect. Natural human teeth have a fluorescent effect, can emit fluorescence under the irradiation of ultraviolet light in a certain wavelength range, contain ultraviolet light components in sunlight, and produce similar ultraviolet light components by artificial light sources in some special occasions. In these cases, if a tooth restoration material without fluorescence or weak fluorescence effect is used, the effect is obviously different from that of the natural tooth, and cannot be coordinated with other natural teeth, so that the simulation effect cannot be achieved. Therefore, only the dental restorative material having a fluorescent effect can achieve an effect close to that of natural teeth. However, the dental restorative materials on the market rarely have an autofluorescence effect, most of the known restorative materials are realized by matching with fluorescent glaze, but the glaze layer is very easy to wear, and can be worn away in several months, but the restoration and coordination effects of teeth are affected, and the glaze layer is thin, and the color of the restoration body can interfere with the fluorescence effect of the glaze layer.
At present, the method for realizing the fluorescent effect of the lithium disilicate glass ceramic mainly comprises the introduction of a fluorescent agent, for example, the fluorescent agent can be introduced through a melting method, and can also be introduced through a sintering method, wherein the fluorescent agent is added in the melting stage, but the matrix material in the fluorescent agent often influences the crystallization process of the glass ceramic material to cause uneven crystallization, so that the light transmittance and the strength of the material are reduced; the latter may have particle size mismatch or refractive index mismatch, resulting in reduced light transmittance, and even some fluorescent agents need to be added in a reducing atmosphere for sintering, which requires high sintering requirements and is difficult to realize industrial production or has high cost.
Disclosure of Invention
The invention provides a starting glass, lithium silicate glass with a core, a preparation method and an application thereof.
In order to achieve the above object, the present invention provides a starting glass comprising or consisting of the following components in percentage by weight: 97 to 99.9 percent of basic glass component and 0.1 to 3 percent of fluorescent component.
Preferably, the base glass component contains or consists of, in weight percent:
SiO2 48-78％
Li2O 12-20.5％
P2O5 0.5-12.5％
K2O 0.5-8％
Al2O3 0.5-6％
ZrO2 0-16％
ZnO 0.5-8.5％
Tb4O7 0.2-3.2％。
in the above-mentioned embodiment, the base glass component may preferably further contain an alkali metal oxide for adjusting the thermal expansion coefficient, usually excluding Li2Alkali metal oxide other than O, the alkali metal oxide being selected from Na2O、K2O、Cs2O、Rb2At least one of O, preferably K2And O. In addition, the base glass component comprises Al whose optical properties, in particular the light transmission, can be adjusted2O3ZnO and yellow capable of adjusting softening point of glass ceramicColorant Tb4O7。
It will be appreciated that the content of each component in the above-mentioned base glass component can be adjusted accordingly as required within the above-mentioned range, for example SiO2May also be 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77% or any point within the above range; li2The content of O may also be 13, 14, 15, 16, 17, 18, 19, 20% or any value within the above range; p2O5May also be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12% or any point within the above range; k2The content of O can also be 1, 2, 3, 4, 5, 6, 7% or any point within the above range; al (Al)2O3The amount of (c) may also be 1, 2, 3, 4, 5% or any value within the above range; ZrO (ZrO)2May also be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15% or any point within the above range; the ZnO content may also be 1, 2, 3, 4, 5, 6, 7, 8% or any value within the above range; tb4O7The content of (c) may also be 0.5, 1, 1.5, 2, 2.5, 3% or any point within the above range.
Preferably, the base glass component contains or consists of, in weight percent:
SiO2 60-72％
Li2O 13-18％
P2O5 2-7％
K2O 2-6％
Al2O3 1-4％
ZrO2 0.5-10％
ZnO 2-6％
Tb4O7 0.3-1.8％。
it is understood that further limiting the content of each component within each of the above ranges can provide the base glass component with better light transmittance.
Preferably, the fluorescent component is selected from oxides, carbonates, nitrates or phosphates of at least two elements of Sm, Dy, Er, Yb, Nd, Tm, Eu. It is understood that the fluorescent component added in the present embodiment is introduced in the form of a compound of a fluorescent element, and no additional fluorescent agent is required. Therefore, in the high-temperature melting process, fluorescent ions can enter the reticular structure of the matrix glass and generate transition under the excitation of light with certain wavelength to emit a fluorescent effect.
Preferably, the composition comprises or consists of the following components in percentage by weight: 98.5 to 99.8 percent of basic glass component and 0.2 to 1.5 percent of fluorescent component. It is understood that the base glass component is 98.6%, 98.7%, 98.8%, 98.9%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7% or any value within the above range, and the content of the fluorescent component can be adjusted within the above range as needed, for example, the amount can be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4% or any value within the above range.
The invention also provides lithium silicate glass with a core, which is obtained by adding a nucleating agent into the basic glass component of the starting glass on the basis of the basic glass component of the technical scheme and then carrying out heat treatment on the basic glass component.
Preferably, the nucleating agent is selected from P2O5、TiO2、Nb2O5、ZrO2At least one of the above-mentioned nucleating agents and any mixture thereof, wherein the addition amount of the nucleating agent is 2-10 wt%. It is understood that the amount of the nucleating agent added can be adjusted within the above range according to the actual situation, and can be, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9% or any point value within the above range.
Preferably, the temperature of the heat treatment is 500-950 ℃, and the treatment time is 3-360 min. It is understood that the temperature of the heat treatment can be adjusted within the above range according to the actual situation, and can be 550, 600, 650, 700, 750, 800, 850, 900 ℃ or any point value within the above range.
The invention also provides a preparation method of the lithium silicate glass with the core according to any one of the technical schemes, which comprises the following steps:
uniformly mixing the basic glass component and the fluorescent component, melting and water quenching, and melting the water-quenched glass frit in an air atmosphere but no reducing atmosphere to obtain glass liquid;
and pouring the obtained glass liquid into a specific mould for forming, cooling the formed ceramic block, and then carrying out heat treatment to obtain the lithium silicate glass with the core.
It is understood that the ceramic block prepared by the above method can be a press ceramic block, for which a restoration with a fluorescent effect can be manufactured by a hot-press casting process, or a CAD ceramic block, for which a restoration with a fluorescent effect (with or without crystallization) can be manufactured by a CAD/CAM process. For both the hot-press casting process and the CAD/CAM process, these are process techniques well known to the person skilled in the art, for example the hot-press casting process may in particular be: preparing a wax pattern of a prosthesis, inserting a casting channel on the wax pattern, embedding, burning a ring after an embedding material is solidified, then putting a press ceramic block and the embedding ring into a die-casting furnace, and pressing the molten press ceramic block into a cavity left after the wax pattern is lost by burning through high temperature; the CAD/CAM process may be: and (4) placing the CAD porcelain block into a processing machine, and processing the corresponding prosthesis by using a lathe needle according to the program. Of course, the specific implementation of the above process is not limited to the above example, and can be implemented in other reasonable ways.
Preferably, the method further comprises the step of adding additives and/or coloring agents in the melting stage of the base glass component and the fluorescent component.
Preferably, the additive is added in an amount of 0 to 17.5% by weight, and the colorant is added in an amount of 0 to 5.5% by weight. It will be appreciated that the above additives and colorants can be adjusted accordingly as desired within the above ranges, for example, the additives can also be added in amounts of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16% or any point within the above ranges; the colorant may also be added at 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5%, or any point within the above ranges.
Preferably, the additive is selected from the group consisting of alkaline earth metal oxides, oxides of trivalent elements, oxides of tetravalent elements, oxides of pentavalent elements and/or oxides of hexavalent elements.
Preferably, the alkaline earth metal oxide is selected from at least one of CaO, BaO, MgO, SrO, and any mixture thereof; the oxide of the trivalent element is except Al2O3Oxides of other trivalent elements selected from B2O3、Y2O3、La2O3、Bi2O3At least one of (a) and any mixtures thereof; the oxide of tetravalent element is SiO2、ZrO2Oxides of other tetravalent elements selected from SnO2、TiO2、GeO2At least one of; the oxide of the pentavalent element is except P2O5Oxides of other pentavalent elements selected from Nb2O5(ii) a The oxide of a hexavalent element is selected from WO3And/or MoO3。
Preferably, the colorant is at least one selected from the group consisting of a yellow colorant, a red colorant and a gray colorant.
Preferably, the yellow colorant is selected from CeO2、Pr2O3、V2O5At least one of zirconium vanadium yellow and zirconium praseodymium yellow; the red colorant is selected from Er2O3At least one of chrome tin red and spinel red pigment; the gray colorant is selected from MnO, NiO and Nd2O3At least one of (1).
Preferably, the base glass component and the fluorescent component are uniformly mixed and melted at 1350-1650 ℃ for 30-120 min. It is understood that the melting temperature and the holding time can be adjusted within the above ranges according to actual conditions, for example, the temperature can also be 1400 ℃, 1450, 1500, 1550, 1600 ℃ or any point value within the above ranges; the holding time may also be 40, 50, 60, 70, 80, 90, 100, 110min or any point within the above range.
Preferably, the temperature for remelting the glass frit is 1350-1650 ℃, and the heat preservation time is 30-120 min. It is understood that the temperature of remelting and the holding time can be adjusted within the above ranges according to the actual situation, for example, the temperature can also be 1400, 1450, 1500, 1550, 1600 ℃, or any point value within the above ranges; the holding time may also be 40, 50, 60, 70, 80, 90, 100, 110min or any point within the above range.
Preferably, the temperature of the heat treatment is 500-950 ℃, preferably 600-900 ℃, and the heat treatment time is 3-360 min. It is understood that the temperature of the heat treatment can be adjusted within the above range according to the actual situation, and can be 550, 600, 650, 700, 750, 800, 850, 900 ℃ or any point value within the above range.
Preferably, the resulting lithium silicate glass having a core comprises a lithium silicate glass and/or a lithium silicate glass ceramic.
The invention also provides application of the lithium silicate glass with the core prepared according to any one of the technical schemes or the preparation method of any one of the technical schemes in preparation of dental restorative materials.
The invention also provides a dental prosthesis which is prepared from the lithium silicate glass with the core according to any one of the technical schemes or the lithium silicate glass with the core prepared by the preparation method according to any one of the technical schemes. It is understood that dental restorations, including but not limited to inlays, onlays, veneers, partial crowns, facets, or abutments, may be made from the lithium silicate glass with a core provided by the present invention.
Compared with the prior art, the invention has the advantages and positive effects that:
the lithium silicate glass with the core is prepared by a melting method, and the lithium silicate glass with the core is prepared by melting basic glass frit and fluorescent components at the same time in a melting stage, quenching the molten glass into glass frit, melting the glass frit into glass liquid, pouring the glass liquid into a mold for molding, and performing heat treatment on the glass liquid. The method introduces the compound of the fluorescent element into the raw materials, does not need to synthesize fluorescent powder, can achieve the required fluorescent effect without reducing atmosphere in the melting process, has simple process, is easy for batch production, and is easy to control the fluorescent color. The prepared lithium silicate glass material can simulate the effect of gradually changing the color of natural teeth from neck to cut off, thereby achieving the fluorescent effect similar to natural teeth and effectively improving the aesthetic effect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 (fusion Process press)
Taking raw material components of the base glass according to the component contents shown in the following table 1, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to be 1350 ℃, melting for 30min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1550 ℃ for 60min, casting the glass frit into a mold for molding, and crystallizing the ceramic block at 900 ℃ in a box-type furnace to obtain the press ceramic block. The press porcelain block can be used for preparing the lithium disilicate glass material restoration with the fluorescent effect by a hot-press casting process.
TABLE 1
| Composition (I) | The content wt% |
| SiO2 | 65 |
| Li2O | 15 |
| P2O5 | 5 |
| K2O | 3 |
| Al2O3 | 3 |
| ZrO2 | 1.3 |
| ZnO | 5 |
| Tb4O7 | 1.2 |
| V2O5 | 0.4 |
| Er2O3 | 0.7 |
| Tm2O3 | 0.2 |
| Eu2O3 | 0.2 |
Example 2 (melting method CAD primary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 2, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to be 1500 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1650 ℃ for 30min, casting into a mold for molding, and crystallizing the ceramic block in a box furnace at 850 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration body with the fluorescent effect by a CAD/CAM process, and crystallization treatment is not needed.
TABLE 2
| Composition (I) | The content wt% |
| SiO2 | 60 |
| Li2O | 14 |
| P2O5 | 4 |
| K2O | 5 |
| Al2O3 | 1 |
| ZrO2 | 0.5 |
| ZnO | 2 |
| Tb4O7 | 0.3 |
| BaO | 2 |
| MgO | 2 |
| La2O3 | 0.2 |
| TiO2 | 2 |
| WO3 | 2 |
| CeO2 | 1.5 |
| MnO | 2 |
| Tm2O3 | 1 |
| Eu2O3 | 0.5 |
Example 3 (melting CAD secondary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 3, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃, melting for 80min, homogenizing the molten glass, and then pouring into cold water to obtain a glass frit; and melting the glass frit at 1350 ℃ for 120min, casting into a mold for molding, and crystallizing the ceramic block in a box furnace at 500 ℃ to obtain the CAD ceramic block. The CAD ceramic block is subjected to CAD/CAM process and crystallization treatment at 900 ℃ at the same time, so that the lithium disilicate glass material restoration with the fluorescent effect can be prepared.
TABLE 3
| Composition (I) | The content wt% |
| SiO2 | 70 |
| Li2O | 13 |
| P2O5 | 2 |
| K2O | 4 |
| Al2O3 | 2 |
| ZrO2 | 0.5 |
| ZnO | 2 |
| Tb4O7 | 0.3 |
| CaO | 2 |
| La2O3 | 0.5 |
| TiO2 | 0.5 |
| Nb2O5 | 0.3 |
| MoO3 | 1 |
| Pr2O3 | 1 |
| NiO | 0.5 |
| Tm2O3 | 0.4 |
Example 4 (fusion Process press)
Taking raw material components of the base glass according to the component contents shown in the following table 4, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1550 ℃ for 80min, casting the glass frit into a mold for molding, and crystallizing the ceramic block in a box-type furnace at 840 ℃ to obtain the press ceramic block. The press porcelain block can be used for preparing the lithium disilicate glass material restoration with the fluorescent effect by a hot-press casting process.
TABLE 4
Example 5 (melting method CAD primary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 5, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to be 1550 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1450 ℃ for 60min, casting into a mold for molding, and crystallizing the ceramic block in a box furnace at 880 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration body with the fluorescent effect by a CAD/CAM process, and crystallization treatment is not needed.
TABLE 5
| Composition (I) | The content wt% |
| SiO2 | 62 |
| Li2O | 14 |
| P2O5 | 7 |
| K2O | 3 |
| Al2O3 | 2 |
| ZrO2 | 2 |
| ZnO | 3 |
| Tb4O7 | 0.6 |
| BaO | 2 |
| MgO | 0.5 |
| SrO | 0.5 |
| La2O3 | 1 |
| Nb2O5 | 0.1 |
| MoO3 | 0.5 |
| CeO2 | 0.4 |
| NiO | 0.6 |
| Nd2O3 | 0.4 |
| Eu2O3 | 0.4 |
Example 6 (melting CAD secondary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 6, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1450 ℃, melting for 30min, homogenizing the molten glass, and then pouring into cold water to obtain a glass frit; and melting the glass frit at 1600 ℃ for 60min, casting into a mold for molding, and crystallizing the ceramic block at 680 ℃ in a box-type furnace to obtain the CAD ceramic block. The CAD ceramic block is subjected to CAD/CAM process and crystallization treatment at 860 ℃, so that the lithium disilicate glass material restoration with the fluorescent effect can be prepared.
TABLE 6
| Composition (I) | The content wt% |
| SiO2 | 61 |
| Li2O | 13 |
| P2O5 | 5 |
| K2O | 6 |
| Al2O3 | 2 |
| ZrO2 | 1 |
| ZnO | 2 |
| Tb4O7 | 1.4 |
| CaO | 2 |
| BaO | 1.3 |
| SrO | 2 |
| TiO2 | 0.5 |
| WO3 | 0.5 |
| V2O5 | 0.5 |
| Er2O3 | 0.5 |
| MnO | 0.5 |
| Dy2O3 | 0.4 |
| Yb2O3 | 0.4 |
Example 7 (fusion Process press)
Taking raw material components of the base glass according to the component contents shown in the following table 7, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to be 1500 ℃, melting for 60min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1400 ℃ for 120min, casting into a mold for molding, and crystallizing the porcelain block at 850 ℃ in a box-type furnace to obtain the press porcelain block. The press porcelain block can be used for preparing the lithium disilicate glass material prosthesis body with the fluorescent effect through a hot-press casting process.
TABLE 7
Example 8 (melting method CAD primary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 8, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1350 ℃ for 30min, casting into a mold for molding, and crystallizing the ceramic block at 900 ℃ in a box-type furnace to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration body with the fluorescent effect by a CAD/CAM process, and crystallization treatment is not needed.
TABLE 8
| Composition (I) | The content wt% |
| SiO2 | 63 |
| Li2O | 13 |
| P2O5 | 2 |
| K2O | 2 |
| Al2O3 | 1 |
| ZrO2 | 10 |
| ZnO | 4 |
| Tb4O7 | 1.1 |
| CaO | 1 |
| MgO | 1 |
| TiO2 | 0.7 |
| V2O5 | 0.5 |
| NiO | 0.5 |
| Tm2O3 | 0.2 |
Example 9 (melting CAD secondary crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 9, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1450 ℃ for 60min, casting into a mold for molding, and crystallizing the ceramic block at 660 ℃ in a box furnace to obtain the CAD ceramic block. The CAD ceramic block is subjected to CAD/CAM process, and crystallization treatment at 840 ℃ is required at the same time, so that the lithium disilicate glass material restoration with the fluorescent effect can be prepared.
TABLE 9
| Composition (I) | The content wt% |
| SiO2 | 62 |
| Li2O | 13 |
| P2O5 | 3 |
| K2O | 4 |
| Al2O3 | 1.5 |
| ZrO2 | 0.5 |
| ZnO | 6 |
| Tb4O7 | 1 |
| CaO | 2 |
| BaO | 2 |
| MgO | 2 |
| SrO | 1 |
| Er2O3 | 0.5 |
| Sm2O3 | 0.5 |
| Eu2O3 | 1 |
COMPARATIVE EXAMPLE 1 (melt method press)
Taking raw material components of the base glass according to the component contents shown in the following table 10, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to be 1500 ℃, melting for 60min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1400 ℃ for 120min, casting into a mold for molding, and crystallizing the porcelain block at 850 ℃ in a box-type furnace to obtain the press porcelain block. The press porcelain block can be used for preparing the lithium disilicate glass material restoration without the fluorescent effect by a hot-press casting process. It should be noted that the content of the fluorescent component deleted in the comparative example was supplemented to the content of ZnO mainly because ZnO did not affect the intensity and transmittance and did not produce a fluorescent effect, as in the following examples.
Watch 10
Comparative example 2 (melting method CAD one-shot crystallization)
Taking raw material components of the base glass according to the component contents shown in the following table 11, selecting oxides, carbonates, phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, melting for 120min, homogenizing the molten glass, and then pouring the molten glass into cold water to obtain a glass frit; and melting the glass frit at 1350 ℃ for 30min, casting into a mold for molding, and crystallizing the ceramic block at 900 ℃ in a box-type furnace to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration without the fluorescent effect by the CAD/CAM process, and crystallization treatment is not needed.
TABLE 11
| Composition (I) | The content wt% |
| SiO2 | 63 |
| Li2O | 13 |
| P2O5 | 2 |
| K2O | 2 |
| Al2O3 | 1 |
| ZrO2 | 10 |
| ZnO | 4.2 |
| Tb4O7 | 1.1 |
| CaO | 1 |
| MgO | 1 |
| TiO2 | 0.7 |
| V2O5 | 0.5 |
| NiO | 0.5 |
Comparative example 3 (sintering CAD secondary crystallization)
Taking the raw material components of the base glass according to the component contents shown in the following table 12, selecting oxides, carbonates or phosphates and the like of the raw materials, and fully and uniformly mixing the raw materials; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃, melting for 40min, homogenizing the molten glass, and then pouring into cold water to obtain a glass frit; the clinker is subjected to coarse grinding and fine grinding until the granularity reaches D50Mixing the ground glass powder and the fluorescent powder into a prepared mould, and carrying out one-time dry pressing molding under the pressure of 100 MPa; the biscuit is sintered in a vacuum atmosphere furnace at 850 ℃ and the vacuum degree is controlled at 500 Pa. The CAD ceramic block can be used for preparing the lithium disilicate glass material restoration with the fluorescent effect through a CAD/CAM process without crystallization treatment.
TABLE 12
| Composition (I) | The content wt% |
| SiO2 | 64 |
| Li2O | 13 |
| P2O5 | 2 |
| K2O | 3.5 |
| Al2O3 | 2 |
| ZrO2 | 1 |
| ZnO | 3 |
| Tb4O7 | 0.5 |
| BaO | 3.5 |
| MgO | 1.2 |
| SrO | 0.8 |
| La2O3 | 1 |
| TiO2 | 1.5 |
| Nb2O5 | 1 |
| WO3 | 0.5 |
| Pr2O3 | 0.6 |
| MnO | 0.4 |
| Fluorescent powder | 0.5 |
TABLE 13 crystal phases corresponding to different heat treatment temperatures in the above examples and comparative examples
| Temperature of primary heat treatment | Corresponding main crystal phase | Temperature of secondary heat treatment | Corresponding main crystal phase | |
| Example 1 | 900 | Lithium disilicate | ||
| Example 2 | 850 | Lithium disilicate | ||
| Example 3 | 500 | Lithium metasilicate | 900 | Lithium disilicate |
| Example 4 | 840 | Lithium disilicate | ||
| Example 5 | 880 | Lithium disilicate | ||
| Example 6 | 680 | Lithium metasilicate | 860 | Lithium disilicate |
| Example 7 | 850 | Lithium disilicate | ||
| Example 8 | 900 | Lithium disilicate | ||
| Example 9 | 660 | Lithium metasilicate | 840 | Lithium disilicate |
| Comparative example 1 | 850 | Lithium disilicate | ||
| Comparative example 2 | 900 | Lithium disilicate | ||
| Comparative example 3 | 850 | Lithium disilicate |
Performance testing
The light transmittance, intensity and fluorescence of the prosthesis prepared in the above examples and comparative examples are tested, and the test results are shown in table 14, and the specific test method is as follows:
the strength test method comprises the following steps: the biaxial bending strength M of each specimen was calculated by the following formula with reference to ISO6872-2015 standard.
In the formula:
m-bending strength, MPa;
w is the maximum load at which the specimen breaks, N;
d, the thickness of the sample at the fracture starting point is mm;
v-poisson's ratio (v is 0.36 for zirconia ceramic materials);
r1-support circle radius, mm;
r2-indenter radius, mm;
r3specimen radius, mm.
The light transmission test method comprises the following steps: reference GBT2680-1994 Standard
The test method is that the sample is made into a sample wafer with phi 14 multiplied by 1.0, and the sample is subjected to full light transmittance measurement by an X-Rite color i7 desk type spectrophotometer. The light source of the instrument is a pulse xenon lamp, the calibration D65 light source has a spectral range of 360-750nm and a wavelength interval of 10 nm. The resolution of the photometry was 0.001%. The transmittance within the range of 6mm of the center diameter of each set of test pieces was measured.
The fluorescence test method comprises the following steps:
the fluorescence effect was visually measured under a UV light box with a wavelength of 365 nm.
TABLE 14 results of the performance test of the restorations obtained in the above examples and comparative preparation
In the table 1, in the comparative examples 1 to 3, the comparative example 1 is a high-transmittance formula without a fluorescent agent, the comparative example 2 is a low-transmittance formula without a fluorescent agent, and the comparative example 3 is a formula with additional fluorescent powder, and it can be known by comparing with the comparative examples 1 and 2 that the prosthesis prepared by the embodiment of the present invention can realize the fluorescent effect while the transmittance and the intensity can satisfy the standards, and compared with the comparative example 3, the prosthesis prepared by the embodiment of the present invention has a more uniform fluorescent effect on the premise that the transmittance and the intensity are not reduced.
Claims (20)
1. The starting glass is characterized by comprising or consisting of the following components in percentage by weight: 97 to 99.9 percent of basic glass component and 0.1 to 3 percent of fluorescent component.
2. The starting glass according to claim 1, wherein the base glass component comprises or consists of, in weight percent:
3. the starting glass according to claim 2, wherein the base glass component comprises or consists of, in weight percent:
4. the starting glass according to claim 1, wherein the fluorescent component is selected from the group consisting of oxides, carbonates, nitrates or phosphates of at least two elements of Sm, Dy, Er, Yb, Nd, Tm, Eu.
5. The starting glass according to claim 1, comprising or consisting of, in weight percent: 98.5 to 99.8 percent of basic glass component and 0.2 to 1.5 percent of fluorescent component.
6. Lithium silicate glass having a core, characterized in that it is obtained by adding a nucleating agent to the base glass component of the starting glass of claim 1 and then heat-treating it.
7. The lithium silicate glass having a core according to claim 6, characterized in that the nucleating agent is selected from the group consisting of P2O5、TiO2、Nb2O5、ZrO2At least one of the above-mentioned nucleating agents and any mixture thereof, wherein the addition amount of the nucleating agent is 2-10 wt%.
8. The lithium silicate glass having a core according to claim 6, wherein the heat treatment temperature is 500-950 ℃ and the heat treatment time is 3-360 min.
9. The method of producing a lithium silicate glass having a core according to any one of claims 6 to 8, characterized by comprising the steps of:
uniformly mixing the basic glass component and the fluorescent component, melting and water quenching, and melting the water-quenched glass frit in an air atmosphere but no reducing atmosphere to obtain glass liquid;
and pouring the obtained glass liquid into a specific mould for forming, cooling the formed ceramic block, and then carrying out heat treatment to obtain the lithium silicate glass with the core.
10. The method of claim 9, further comprising the step of adding additives and/or colorants during the melting stage of the base glass component and the fluorescent component.
11. The method according to claim 10, wherein the additive is added in an amount of 0 to 17.5% by weight and the colorant is added in an amount of 0 to 5.5% by weight.
12. The process according to claim 10 or 11, characterized in that the additive is chosen from alkaline earth metal oxides, oxides of trivalent elements, oxides of tetravalent elements, oxides of pentavalent elements and/or oxides of hexavalent elements.
13. The method according to claim 12, wherein the alkaline earth metal oxide is selected from at least one of CaO, BaO, MgO, SrO, and any mixture thereof; the oxide of the trivalent element is except Al2O3Oxides of other trivalent elements selected from B2O3、Y2O3、La2O3、Bi2O3At least one of (a) and any mixtures thereof; the oxide of tetravalent element is SiO2、ZrO2Oxides of other tetravalent elements selected from SnO2、TiO2、GeO2At least one of; the oxide of the pentavalent element is except P2O5Five othersOxides of valence elements selected from Nb2O5(ii) a The oxide of a hexavalent element is selected from WO3And/or MoO3。
14. The method according to claim 10 or 11, wherein the colorant is at least one selected from a yellow colorant, a red colorant and a gray colorant.
15. The method of claim 14, wherein the yellow colorant is selected from CeO2、Pr2O3、V2O5At least one of zirconium vanadium yellow and zirconium praseodymium yellow; the red colorant is selected from Er2O3At least one of chrome tin red and spinel red pigment; the gray colorant is selected from MnO, NiO and Nd2O3At least one of (1).
16. The manufacturing method according to claim 9, wherein the base glass component and the fluorescent component are uniformly mixed and melted at 1350 ℃ to 1650 ℃ for 30min to 120 min.
17. The method of claim 9, wherein the glass frit is remelted at a temperature of 1350 ℃ to 1650 ℃ for a time of 30 to 120 min.
18. The method of any one of claims 9 to 17, wherein the resulting lithium silicate glass having a core comprises a lithium silicate glass and/or a lithium silicate glass ceramic.
19. Use of a lithium silicate glass with a core according to any one of claims 6 to 8 or a lithium silicate glass with a core produced by the production method according to any one of claims 9 to 18 for the production of dental restorative materials.
20. Dental prosthesis, characterized in that it is made of a lithium silicate glass with a core as described in any of claims 6 to 8 or a lithium silicate glass with a core as produced by the production method described in any of claims 9 to 18.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113264684A (en) * | 2021-06-11 | 2021-08-17 | 辽宁爱尔创生物材料有限公司 | Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration |
| CN113443813A (en) * | 2021-05-27 | 2021-09-28 | 上海硕密新材料科技有限公司 | Distributed glass product production process |
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| CN113443813A (en) * | 2021-05-27 | 2021-09-28 | 上海硕密新材料科技有限公司 | Distributed glass product production process |
| WO2022257624A1 (en) * | 2021-06-11 | 2022-12-15 | 辽宁爱尔创生物材料有限公司 | Dental lithium silicate glass ceramic and preparation method therefor, and lithium silicate glass ceramic prosthesis |
| CN113264684A (en) * | 2021-06-11 | 2021-08-17 | 辽宁爱尔创生物材料有限公司 | Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration |
| CN113461336A (en) * | 2021-06-18 | 2021-10-01 | 辽宁爱尔创生物材料有限公司 | Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration |
| WO2022262419A1 (en) * | 2021-06-18 | 2022-12-22 | 辽宁爱尔创生物材料有限公司 | Dental lithium silicate glass ceramic, preparation method therefor, and lithium silicate glass ceramic prosthesis |
| CN113603365A (en) * | 2021-09-03 | 2021-11-05 | 北京赢冠口腔医疗科技股份有限公司 | Lithium silicate microcrystalline glass, decorative ceramic powder, preparation method of decorative ceramic powder and metal porcelain tooth |
| CN113754288A (en) * | 2021-09-08 | 2021-12-07 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof |
| CN113754288B (en) * | 2021-09-08 | 2023-01-03 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof |
| WO2023035692A1 (en) * | 2021-09-08 | 2023-03-16 | 深圳爱尔创口腔技术有限公司 | Ion exchange enhanced fluorescent lithium silicate glass ceramic and preparation method therefor |
| CN114477772A (en) * | 2022-01-30 | 2022-05-13 | 山东国瓷功能材料股份有限公司 | High-strength, high-permeability glass-ceramic structure, preparation method and product thereof |
| CN114477772B (en) * | 2022-01-30 | 2023-07-25 | 山东国瓷功能材料股份有限公司 | High-strength high-permeability glass ceramic structure, preparation method thereof and obtained product |
| CN114605075A (en) * | 2022-03-30 | 2022-06-10 | 山东国瓷功能材料股份有限公司 | Fluorescent glass ceramic containing cadmium tungstate crystal phase |
| CN114790082A (en) * | 2022-03-30 | 2022-07-26 | 山东国瓷功能材料股份有限公司 | Fluorescent glass ceramic containing zinc tungstate crystal phase |
| CN115721565A (en) * | 2022-12-05 | 2023-03-03 | 北京赢冠口腔医疗科技股份有限公司 | Tooth veneer cutting porcelain, preparation method thereof and tooth veneer |
| CN118993531A (en) * | 2024-08-16 | 2024-11-22 | 南京神童特种玻璃技术有限公司 | Silicate glass with high zirconia content and preparation method and application thereof |
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